Macromol. Chem. Phys., Vol. 196,
No. 10, pp. 3267-3280, 1995
MACROMOLECULAR DIVISION
COMMISSION ON POLYMER CHARACTERIZATION AND PROPERTIES
Working Party on Modeling of Polymerization Kinetics and Processes
Critically Evaluated Rate Coefficients
For Free-Radical Polymerization - 1. Propagation Rate Coefficient For
Styrene
M. Buback, R.G. Gilbert, R.A. Hutchinson, B. Klumperman, F.D. Kuchta,
B.G. Manders, K.F. Odriscoll, G.T. Russell, J. Schweer
Synopsis: Pulsed-laser polymerization (PLP) in conjugation with
molecular weight distribution (MWD) measurement has emerged as the method
of choice for determining the propagation rate coefficient k(p) in free-radical
polymerizations. Detailed guidelines for using this technique (including
essential internal consistency checks) and reporting the results therefrom
are given by the authors, members of the IUPAC Working Party on Modeling
of kinetics and processes of polymerization. The results for PLP-MWD
k(p) measurements from many laboratories for bulk free-radical polymerization
of styrene at low conversions and ambient pressure are collated, and
are in excellent agreement. They are therefore recommended as constituting
a benchmark data set, one that is best fitted by
k(p) = 10(7.630) L . mol(-1) . s(-1) exp (-32.51 kJ . mol(-1) / R .
T)
(the confidence ellipsoid for the Arrhenius parameters is also given).
These benchmark data are also used to evaluate the merits of several
other methods for determining k(p); it is found that appropriately calibrated
electron paramagnetic resonance spectroscopy appears to yield reliable
values of k(p) for styrene.
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